JP6903169B2 - BODIPY compounds for use in display devices - Google Patents

Description

(Technical field)
The present embodiment includes compounds for use in color filters through which light passes.

In color reproduction, the gamut is a subset of a particular perfect color. The most common usage refers to a subset of colors that can be accurately represented in a particular situation, such as in a particular output device. For example, the wide color gamut Red Green Blue (RGB) color space (or Adobe Wide Gamut RGB) is an RGB color space developed by Adobe Systems that uses pure spectral primary colors to provide a large color gamut. It is said that a wider range of color values can be stored than in the sRGB or Adobe RGB color space. Therefore, it is considered that a display device capable of providing a wider color gamut can express more vivid colors.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^２’、Ｒ^５’、Ｒ^６’、Ｒ^３”、Ｒ^４”、Ｒ^５”、およびＲ^６”は、独立して、ＨまたはＣ１−３アルキルなどの置換基である。Ｌ^１は、Ｆ、Ｃｌ、Ｂｒ、またはＩであり、Ｌ^２は任意に置換されたシクロペンタジエンアニオンである。 Some embodiments include coordination complexes represented by the formula:

In the formula, R ¹ , R ^2, R ³ , R ⁵ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ^6" are , Independently, substituents such as H or C1-3 alkyl. L ¹ is F, Cl, Br, or I and L ² is an arbitrarily substituted cyclopentadiene anion.

In some embodiments, coordination complexes comprising optionally substituted 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene and iridium, such as the compounds shown in the above paragraph, and It comprises an optical filter containing a polymer matrix, in which case the coordination complex is placed within the polymer matrix. Here, the optical filter has a quantum yield of less than about 1%.

Some embodiments include a display device comprising an optical filter described herein and an RBG light source arranged so that the RGB light source can be viewed through the optical filter.

FIG. 1 is a schematic diagram of an example of a display device having a filter containing the compounds described herein. FIG. 2 is a graph showing a normalized absorption spectrum of a film containing Ir-BODIPY complex 1.

Detailed description of the invention

One of the problems with the wide color gamut is that the green and red colors may be spectrally adjacent to each other and completely indistinguishable from each other. One way to reduce these chromatic aberrations is to use an absorbent dye to reduce the amount of spectral radiation and overlap in this region. In some cases, wavelength conversion materials can be incorporated into display device filters. Furthermore, in order to reduce the effect of synchrotron radiation removal while sharpening the perceived distinction between green and red colors, a narrow absorption spectrum, as indicated by the narrow full width at half maximum (FWHM), may be desirable.

Boron dipyrromethene (BODIPY) is a type of near-infrared dye. They can be fluorescent materials and can be included in the polymer matrix. However, these compounds have some potential problems.

One problem is that because it is a fluorescent compound, the emission of BODIPY can compete with the RBG source of the display device. A possible solution to these problems is to extinguish the fluorescence of the compound by altering the structure of the compound or by binding it to a transition metal complex to alter its luminescence properties. However, the absorption of these compounds can coincide with the emission wavelength of green light, which is inconsistent with the projection or display of green light. In addition, the non-radioactivity of the excited BODIPY solution does not necessarily result in an excited film having the same or similar non-radioactivity.

By adopting a newly designed molecular structure, as in the example shown below, we report new materials that can be used in filter and display device applications. The BODIPY compounds described herein have one or more of the following desirable properties: low or essentially no quantum yield, high absorbance, and / or narrow half width at maximum absorbance.

Some filters containing the BODIPY compounds described herein can reduce fluorescence, eg, less than about 10% (or 0.1), less than about 5% (or 0.05), about 3. Less than% (or 0.03), less than about 2% (or 0.02), less than about 1% (or 0.01), less than about 0.8% (or 0.008), about 0.7% (or about 0.7%) Or less than 0.007), less than about 0.5% (or 0.005), less than about 0.4% (or 0.004), less than about 0.2% (or 0.002), or about 0. Less than 1% (or 0.001). Therefore, they are particularly useful dyes for color correction of display devices, improvement of color purity, or expansion of color reproduction range. Measurement of the quantum yield in solution is the integrated fluorescence emission of the BODIPY compounds and / or BODIPY Ir complexes described herein with Nile Blue A (QY = 0 in ethanol) with equal dye absorbance at excitation wavelength conversion. This can be done by comparing with the integrated fluorescence of .23). Polymer-only fluorescence is subtracted from the sample fluorescence for each measurement. The quantum yield of the film can also be determined using a quantum yield spectrophotometer, such as a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA). In some embodiments, the BODIPY-iridium compounds described herein can be weakly fluorescent or essentially non-fluorescent.

BODIPY compounds of the formula below are above about 515 nm or above about 520 nm, eg, above about 522 nm, about 500-600 nm, about 510-550 nm, about 510-530 nm, about 530-550 nm, about 510-520 nm, about. It can be a compound that effectively and selectively absorbs light in the region of 515-520 nm, about 520-525 nm, about 525-530 nm, about 530-540 nm, or about 540-550 nm. The range containing the next peak absorption is particularly important: about 520 nm, about 522 nm, about 525 nm.

In some embodiments, for example, the shoulder of the absorption spectrum of about 475 nm in FIG. 2 can be removed and / or reduced by modifying the chemical structure of the compound to be stiffer, and thus vibration in absorption. Limit the rotation that can cause the property. This is reflected as a shoulder as a spectrum.

In some applications, such as helping to distinguish between green and red, BODIPY compounds are, for example, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 20-50 nm, The full width at half maximum may be particularly narrow, such as the full width at half maximum within a range delimited by about 20-30 nm, about 30-40 nm, about 40-50 nm, or any of these values.

The optical filters described herein typically include coordination complexes dispersed within a polymer matrix.

In general, the coordination complexes described herein are optionally substituted 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacen (BODIPY) for use in optical filters or other applications. ) And transition metals such as iridium. In addition to optionally substituted BODIPY, transition metals such as iridium may be coordinated to other ligands.

Any suitable transition metal such as V, Cu, Fe, Ir, Pt, Rh, Os, and / or Re can be used. In some embodiments, the transition metal is Ir.

BODIPY has the structure shown in Equation 1.

Unless otherwise stated, when a compound or chemical structural feature, such as aryl, is referred to as "arbitrarily substituted," it has a substituent-free (ie, unsubstituted) feature, or has one or more substituents. Includes "replaced" features. The term "substituent" has the broadest meaning known to those of skill in the art and includes a moiety that occupies a position normally occupied by one or more hydrogen atoms attached to a parent compound or structural feature. In some embodiments, the substituent can be a conventional organic moiety known in the art, which is 15-50 / mol, 15-100 g / mol, 15-200 g / mol, or 15-500 g. It can have a molecular weight of / mol (eg, the sum of the atomic masses of the atoms of the substituents). Some substituents include F, Cl, Br, I, NO ₂ , C _1-12 H _3-25 , C _1-12 H _1-25 O, C _1-12 H _1-25 O ₂ , C. _1-12 H _3-26 N, C _1-12 H _1-26 NO, C _1-12 H _3-27 N ₂ , C _1-12 F _3-25 , optionally substituted phenyl, substituted Included may be naphthyl, optionally substituted C _3-10 heteroaryl, and the like.

For convenience, the term "molecular weight" is used to refer to the sum of the atomic masses of the atoms of a part or part of a molecule, even if it is not a complete molecule.

The formula numbers can be used to identify the location of hydrogen or substituents on the BODIPY parent structure. For example, when position 1 contains a methyl substituent, the carbon atom represented by "1" is directly attached to the methyl substituent, as in the compounds shown below.

For any BODIPY structure, position 1 represented in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl such as _{C 1} alkyl, C ₂ alkyl, C ₃ alkyl, F, Cl, Br, Halo such as I _{, fluoroalkyl such as CF 3} and the like may be included.

For any BODIPY structure, position 2 represented in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl such as _{C 1} alkyl, C ₂ alkyl, C ₃ alkyl, F, Cl, Br. , I halo, CF _{3 and the} like, fluoroalkyl and the like may be included.

For any BODIPY structure, position 3 represented in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl such as _{C 1} alkyl, C ₂ alkyl, C ₃ alkyl, F, Cl, Br. , I halo, CF _{3 and the} like, fluoroalkyl and the like may be included.

For any BODIPY structure, position 5 shown in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl, F, Cl _{such as C 1} alkyl, C ₂ alkyl, C ₃ alkyl. , Br, halos such as I _{, fluoroalkyls such as CF 3} and the like may be included.

For any BODIPY structure, position 6 represented in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl such as _{C 1} alkyl, C ₂ alkyl, C ₃ alkyl, F, Cl, Br. , I halo, CF _{3 and the} like, fluoroalkyl and the like may be included.

For any BODIPY structure, position 7 represented in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl such as _{C 1} alkyl, C ₂ alkyl, C ₃ alkyl, F, Cl, Br. , I halo, CF _{3 and the} like, fluoroalkyl and the like may be included.

For any BODIPY structure, position 8 represented in Formula 1 is a substituent such as H, or alkyl, eg, _{C 1-3} alkyl such as _{C 1} alkyl, C ₂ alkyl, C ₃ alkyl, F, Cl, Br. , I halo, CF _{3 and the} like, optionally substituted phenyl, optionally substituted 4- (pyridin-2-yl) phenyl and the like optionally substituted aryl and the like. In some embodiments, position 8 may comprise 4- (pyridin-2-yl) phenyl), as shown in Formula 2 below.

For 4- (pyridin-2-yl) phenyl at position 8 of the BODIPY structure, position 2'represented in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C ₃ alkyl. _{It may contain C 1-3} alkyl such as C 1-3 alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For 4- (pyridin-2-yl) phenyl at position 8 of the BODIPY structure, position 3'represented in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C ₃ alkyl. _{It may contain C 1-3} alkyl such as C 1-3 alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For 4- (pyridin-2-yl) phenyl at position 8 of the BODIPY structure, position 5'represented in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C ₃ alkyl. _{It may contain C 1-3} alkyl such as C 1-3 alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For any 4- (pyridin-2-yl) phenyl at position 8 of the BODIPY structure, position 6'represented in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, _{C 1-3} alkyl, such as C ₃ alkyl, F, Cl, Br, halo such as I, may include a fluoroalkyl such as CF _3.

With respect to 4- (pyridin-2-yl) phenyl at position 8 of the BODIPY structure, position 3 "represented in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C ₃ alkyl. _{It may contain C 1-3} alkyl such as C 1-3 alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For any 4- (pyridin-2-yl) phenyl at the 8-position of the BODIPY structure, the 4 "position shown in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C. _{It may include C 1-3} alkyl such as 3 alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For any 4- (pyridin-2-yl) phenyl at the 8-position of the BODIPY structure, the 5-position shown in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C _{3 It may include C 1-3} alkyl such as alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For any 4- (pyridin-2-yl) phenyl at the 8-position of the BODIPY structure, the 6-position shown in Formula 1 is a substituent such as H, or alkyl, eg, C ₁ alkyl, C ₂ alkyl, C _{3 It may include C 1-3} alkyl such as alkyl, halo such as F, Cl, Br, I, fluoroalkyl such as _{CF 3.}

For related structural representations such as formula 1 or 2, substituents such as H or position 1, position 2 shown in the table below may be referred to as ^{R 1} , R ^{2 and the like.}

Some BODIPY ligands are represented by the following equations.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^２’、Ｒ^３’、Ｒ^５’、Ｒ^６’、Ｒ^３”、Ｒ^４”、Ｒ^５”、およびＲ^６”は、独立して、ＨまたはＣ_１−３アルキルなどの置換基である。

In the formula, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ² ', R ³ ', R ⁵ ', R ⁶ ', R ³ ", R ⁴ ", R ⁵ ", and R ⁶ "is independently a substituent such as _{H or C 1-3 alkyl.}

The optionally substituted BODIPY ligand may be coordinated at two positions with respect to the iridium metal. In some embodiments, the iridium metal coordinates with at least one nitrogen atom of the optionally substituted BODIPY ligand.

In some embodiments, the BODIPY ligand is optionally substituted 8- (4- (pyridin-2-yl) phenyl) -4,4-difluoro-4-bora-3a, 4a-diaza-s-. Indasen.

In addition to the optionally substituted BODIPY, the coordination complexes described herein may contain another 1, 2, or 3 ligands. In some embodiments, the coordination complex comprises optionally substituted BODIPY and two additional ligands. Iodide, bromide, sulfide, thiocyanate, chloride, nitrate, azide, fluoride, hydroxide, oxalate, water, nitrite, isothiocyanate, acetonitrile, pyridine, ammonia, ethylenediamine, 2, 2'-bipyridine, 1,10-phenanthroline, nitrite, triphenylphosphine, cyanide, carbon monoxide, acetylacetonate, alken, aminopolycarboxylic acid, 1,2-bis (o-aminophenoxy) ethane-n , N, n', n'-tetraacetic acid, benzene, 1,2-bis (diphenylphosphino) ethane, 1,1-bis (diphenylphosphino) methane, corol, crown ether, 2,2,2-cryptand , Cryptoate, cyclopentadienyl anion, diethylenetriamine, dimethylglycimate, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, diethylenetriaminetetraacetic acid (pentetic acid), ethylenediaminetetraacetic acid Acetic acid, ethylenediaminetriacetic acid, ethyleneglycolbis (oxyethylenediaminetrilo) tetraacetic acid, hula-2, glycineto (glycinato), hem, iminodiacetic acid, nicotianamine, nitrosyl, nitrilotriacetic acid, oxo, pyrazine, scorpion acid ligand, 2,2'; 6', 2''-terpyridine, triazacyclononane, tricyclohexylphosphine, triethylenetetramine, trimethylphosphine, tri (o-tolyl) phosphine, tris (2-aminoethyl) amine, tris (2) Any suitable ligand, such as an anion, Lewis base, or unsaturated compound, such as −diphenylphosphineethyl) amine, tropylium, carbon dioxide, etc. may be used. In some embodiments, the ligand is a halogen such as F, Cl, Br, I; or an optionally substituted aryl anion such as cyclopentadienyl anion. In some embodiments, the 1, 2, or 3 ligand is Cl. In some embodiments, one ligand is Cl. In some embodiments, the 1, 2, or 3 ligands are optionally substituted cyclopentadienyl anions, such as pentamethylcyclopentadienyl anions. In some embodiments, the ligand is a pentamethylcyclopentadienyl anion.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^２’、Ｒ^５’、Ｒ^６’、Ｒ^３”、Ｒ^４”、Ｒ^５”、およびＲ^６”は独立してＨまたはＣ_１−３アルキルなどの置換基である。Ｌ^１は、Ｆ、Ｃｌ、Ｂｒ、Ｉなどのリガンドである。Ｌ^２は、任意に置換されたシクロペンタジエニルアニオンなどのリガンドである。 In some embodiments, the coordination complex is represented by a formula:

In the formula, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ² ', R ⁵ ', R ⁶ ', R ³ ", R ⁴ ", R ⁵ ", and R ⁶ " are Independently, it is a substituent such as _{H or C 1-3 alkyl.} L ¹ is a ligand such as F, Cl, Br, I and the like. L ² is a ligand such as an arbitrarily substituted cyclopentadienyl anion.

For related structural representations such as formula 3 or 4, in some embodiments, R ¹ is C 1-3 alkyl, R ² is C _1-3 alkyl, R ³ is C _1-3 alkyl, and R ⁵ is C _{1. -3} alkyl, ^{R 6} is _{C 1-3,} ^{R 7} is _{C 1-3} alkyl, R ^{2 'is} H or _{C 1-3} alkyl, R ^5' is H or _{C 1-3} alkyl, ^{R 6 'is} H or _{C 1-3} alkyl, R ^3''is H or _{C 1-3} alkyl, ^{R 4 "is} H or _{C 1-3} alkyl, ^{R 5"} is H or _{C 1-3} alkyl, ^{R 6 "} Is H or C _1-3 alkyl.

For related structural representations such as formula 3 or 4, in some embodiments R ¹ is H. In some embodiments, R ¹ is CH ₃ . In some embodiments, R ¹ is C ₂ alkyl. In some embodiments, R ¹ is C ₃ alkyl. In some embodiments, R ¹ is H, C ₂ alkyl, or C ₃ alkyl. And R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ^6" are independently H. Or C _1-3 alkyl.

For related structural representations such as formula 3 or 4, in some embodiments R ³ is H. In some embodiments, R ³ is CH ₃ . In some embodiments, R ³ is C ₂ alkyl. In some embodiments, R ³ is C ₃ alkyl. In some embodiments, R ³ is H, C ₂ alkyl, or C ₃ alkyl. And R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ^6" are independently H. Or C _1-3 alkyl.

For related structural representations such as formula 3 or 4, in some embodiments R ⁵ is H. In some embodiments, R ⁵ is CH ₃ . In some embodiments, ^{R 5} is _{C 2} alkyl. In some embodiments, ^{R 5} is _{C 3} alkyl. In some embodiments, ^{R 5} is H, _{C 2} alkyl or _{C 3} alkyl. R ¹ , R ² , R ³ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ⁶ " are independently H or C. It is _{1-3 alkyl.}

For related structural representations such as formula 3 or 4, in some embodiments R ⁷ is H. In some embodiments, R ⁷ is CH ₃ . In some embodiments, R ⁷ is C ₂ alkyl. In some embodiments, R ⁷ is a C ₃ alkyl. In some embodiments, R ⁷ is H, C ₂ alkyl, or C ₃ alkyl. And R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ^6" are independently H. Or C _1-3 alkyl.

For related structural representations such as formula 3 or 4, in some embodiments R ² is CH ₂ CH ₃ . In some embodiments, R ² is C _1-3 alkyl. R ¹ , R ³ , R ⁵ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ^6" are independently H or C. It is _{1-3 alkyl.}

For related structural representations such as formula 3 or 4, in some embodiments R ⁶ is CH ₂ CH ₃ . In some embodiments, ^{R 6} is _{C 1-3} alkyl. R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^{3 "} , R ^4" , R ^{5 "} , and R ^6" are independently H or C. It is _{1-3 alkyl.}

For related structural representations such as formula 3 or 4, in some embodiments, at least one of ^{R 1} , R ³ , R ⁵ , and R ⁷ is not _{CH 3.}

For related structural representations such as formula 3 or 4, in some embodiments, at least one of ^{R 2} and R ^{6 is not H.}

For related structural representations such as formula 3 or 4, in some embodiments, at least one of ^{R 1} , R ³ , R ⁵ , and R ⁷ is not _{CH 3} , or at least one of ^{R 2} and R ^6. One is not H.

In some embodiments, the coordination complex is not:

Some coordination complex, two non-BODIPY ligands, for example, L ¹ and L ² may be pyridinylmethoxy phenyl-based and non-planar ligand as shown in Formula 3 or Formula 4. For example, the dihedral angle between the pyridinylphenyl-Ir plane and the L1-Ir-L2 plane can be greater than 45 °, 75 °, 80 °, and / or 90 °. In some embodiments, the dihedral angle between the pyridinylphenyl-Ir plane and the L1-Ir-L2 plane is about 80-100 °, about 85-95 °, or about 90 °.

、またはエナンチオマーなどの立体異性体、またはそれらのジアステレオマーまたはラセミ混合物。 One useful coordination complex is:

, Or stereoisomers such as enantiomers, or diastereomers or racemic mixtures thereof.

The polymer matrix includes acrylic, polycarbonate, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer or saponification product thereof, AS, polyester, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinylphosphonic acid (PVPA). ), Polyester, phenolic resin, phenoxy resin, polysulfone, nylon, cellulose resin, cellulose acetate, etc., composed of or include any suitable polymer. In some embodiments, the polymer is an acrylic or acrylate polymer. In some embodiments, the polymer matrix comprises poly (methyl methacrylate).

The oxygen scavenger may be present, for example, in the polymer matrix. Helps reduce the oxidation of the coordination complex. This may improve the color stability of the filter.

The filter may have any suitable configuration in which the coordination complex is dispersed within the polymer matrix. In some embodiments, the polymer matrix functions as a binder resin. Typical examples of filter configurations include a laminated structure consisting of a transparent sheet or film substrate and a layer containing a compound dispersed in a polymer acting as a binder resin, and a single layer structure, for example, a binder resin containing a compound. Includes sheet or film.

In some embodiments, the polymer matrix containing the coordination complex is about 0.1-100 μm, about 0.1-20 μm, about 20-40 μm, about 40-60 μm, about 60-100 μm, about 0.1 μm-. It is in the form of a layer having a thickness of about 50 μm, or about 30 μm – about 100 μm.

When two or more BODIPY compounds are used, they can be mixed into a single layer or single film of the laminate, or can provide multiple layers or films each containing the compound. In this case, a laminate is formed even in the latter case described above. The characteristics of the filter can be adjusted by adjusting the binder resin according to each BODIPY used in the resin.

The laminated filter is, for example, a method in which (1) a compound and a binder resin are dissolved or dispersed in an appropriate solvent, coated or dispersed on a transparent sheet or a film substrate by a conventional method, and then dried, and (2) a compound. A method in which a binder resin is melt-kneaded, a mixture is formed into a film or a sheet by a conventional molding technique of a thermoplastic resin such as extrusion, injection molding, and compression molding, and the film is bonded to a transparent base material, for example, with an adhesive. (3) A method including extruding and laminating a melt mixture of a BODIPY compound and a binder resin onto a transparent substrate, and (4) Simultaneously extruding a melt mixture of a BODIPY compound and a binder resin together with a melted resin for a transparent substrate. The method, or (5) the method of molding the binder resin into a film or sheet by extrusion, injection molding, or compression, in which the film or sheet is brought into contact with a solution of the BODIPY compound by molding or the like, and thus the film or sheet dyed. Can be produced by, for example, adhering to a transparent substrate with an adhesive.

A single-layer sheet or film containing a resin containing a BODIPY compound may be, for example, (1) a method of casting a solution or dispersion of a BODIPY compound and a binder resin in a suitable solvent onto a carrier and then drying, (2) BODIPY. A method of melt-kneading a compound and a binder resin and molding the mixture into a film or sheet by a conventional molding technique of a thermoplastic resin such as extrusion, injection molding, compression molding, or (3) extrusion, injection molding, compression molding, etc. The binder resin is molded into a film or sheet and is manufactured by a method comprising contacting the film or sheet with a solution of a BODIPY compound.

The laminated filter can include a transparent substrate having a BODIPY compound-containing resin layer arranged on the surface of the transparent substrate. The BODIPY compound-containing resin layer can include a binder resin and a BODIPY compound dispersed in the binder resin. This type of laminate filter is a coating composition in which a BODIPY compound and a binder resin are dissolved in an appropriate solvent, or particles of a compound having a particle size of 0.1-3 micrometer (μm) and a binder resin are dispersed in the solvent. Can be produced by coating a transparent sheet or a film substrate and drying the coating film.

The method of making the filter can be selected according to the layer structure and material suitable for a specific application.

The materials of the transparent substrates that can be used for LCD and / or PDP filters are not particularly limited as long as they are substantially transparent, have little light absorption and little light scattering. Examples of suitable materials include glass, polyolefin resins, amorphous polyolefin resins, polyester resins, polycarbonate resins, acrylic resins, polystyrene resins, polyvinyl chloride resins, polyvinyl acetate resins, polyarylate resins, and polyether sulfone resins. Is done. Suitable examples include poly (methyl methacrylate) (PMMA).

The resin can be molded into a film or sheet by conventional molding methods such as injection molding, T-die extrusion, calendering and compression molding, and / or by casting a solution of the resin in an organic solvent. The resin can include commonly known additives such as thermal anti-aging agents, lubricants, sweeping agents, antioxidants and the like. The thickness of the substrate is 10 micrometers (μm) to 5 mm. The resin film or sheet may be an unstretched or stretched film or sheet. The base material may be a laminate of the above material and another film or sheet.

If desired, the transparent substrate can be subjected to known surface treatments such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, or chemical treatment. If desired, the substrate can be coated with an anchor or primer.

Solvents that can be used to dissolve or disperse dyes and resins include alkanes such as butane, pentane, hexane, heptane, octane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptan, cyclooctane; ethanol, propanol, butanol, Alcohols such as amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, furfuryl alcohol; cellosolves such as methylcellosolve, ethylserosolve, butylcellosolve, methylcellosolve acetate, ethylserosolve acetate. Propylene glycol and its derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; acetone, acetone. , Methylamyl ketone, cyclohexanone, acetophenone and other ketones; ethers such as dioxane and tetrahydrofuran; butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl acid, ethyl acid, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, Esters such as ethyl lactate, methyl 3-methoxypropionate; halogenated hydrocarbons such as chloroform, methylene chloride, tetrachloroethane; aromatic hydrocarbons such as benzene, toluene, xylene, cresol. Highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone may be included.

An RGB source is a light source that emits red, green, and blue light at the same time. Such sources are primarily needed for color display applications. A wide range of colors can be obtained by mixing different amounts of red, green, and blue light (additive color mixing). Suitable RGB sources include, but are not limited to, brown tubes (CRTs), liquid crystal displays (LCDs), plasma displays, or organic light emitting diode (OLED) displays such as televisions, computer monitors, or large scale screens. Each pixel on the screen can be constructed by driving three small, very close, but still separated RGB light sources. At a common viewing distance, different sources can appear indistinguishable, which can be deceptive to seeing a particular single color. All pixels placed together on a rectangular screen surface fit the color image.

FIG. 1 shows an example of the configuration of a device containing the compounds described herein. The device 10 may include the following layers in a predetermined order: filter layer 15 and display layer 20. In some embodiments, the display layer can be the outermost layer or surface of a display device, eg, an RGB source. Suitable RGB light sources can be liquid crystal display devices, plasma display panels, and / or cathode ray terminals. In some embodiments, the filter layer 15 can be placed, for example, distal to or outside the RGB source so that the viewer can see the RGB source through it. In some embodiments, viewing the RGB source through the filter layer can increase the color distinction between the red and green colors.

式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^２’、Ｒ^５’、Ｒ^６’、Ｒ^３’’、Ｒ^４’’、Ｒ^５’’、およびＲ^６’’は独立してＨまたはＣ_１−３アルキルであり、Ｌ^１はＦ、Ｃｌ、Ｂｒ、またはＩであり、Ｌ^２は任意に置換されたシクロペンタジエンアニオンであり、式中、Ｒ^１、Ｒ^３、Ｒ^５、およびＲ^７の少なくとも１つはＣＨ_３ではなく、またはＲ^２およびＲ^６の少なくとも１つはＨではない。
（実施形態２）
Ｒ^２がＣ_１−３アルキルである、実施形態１に記載の配位錯体。
（実施形態３）
Ｒ^６がＣ_１−３アルキルである、実施形態１または２に記載の配位錯体。
（実施形態４）
実施形態１に記載の配位錯体、つまり、

またはそれらの混合物。
（実施形態５）
任意に置換された４，４−ジフルオロ−４−ボラ−３ａ，４ａ−ジアザ−ｓ−インダセンおよびイリジウムを含む配位錯体、および
ポリマーマトリックス
を含む光学フィルターであって、前記配位錯体が前記ポリマーマトリックス内に分散しており、
前記フィルターは約１％未満の量子収率を有する、光学フィルター。
（実施形態６）
実施形態１、２、３、または４に記載の配位錯体、および
ポリマーマトリックス
を含む光学フィルターであって、前記配位錯体はポリマーマトリックス内に配置されており、
前記フィルターは約１％未満の量子収率を有する、光学フィルター。
（実施形態７）
前記ポリマーマトリックスがポリ（メチルメタクリレート）（ＰＭＭＡ）を含む、実施形態５または６に記載の光学フィルター。
（実施形態８）
前記ポリマーマトリックスが、約０．１μｍ〜約５０μｍの厚さを有する層の形態である、実施形態５、６、または７に記載の光学フィルター。
（実施形態９）
前記フィルターが、約５１５ｎｍより大きいピーク吸収を有する、実施形態５、６、７、または８に記載の光学フィルター。
（実施形態１０）
前記フィルターが約５２２ｎｍより大きいピーク吸収を有する、実施形態９に記載の光学フィルター。
（実施形態１１）
前記フィルターが、約５０ｎｍ未満の半値全幅（ＦＷＨＭ）を有する、実施形態５、６、７、８、９、または１０に記載の光学フィルター。
（実施形態１２）
前記フィルターが、約２０〜約３０ｎｍのＦＷＨＭを有する、実施形態１１に記載の光学フィルター。
（実施形態１３）
実施形態５、６、７、８、９、１０、１１、または１２に記載の光学フィルターと、前記光学フィルターを通してＲＧＢ光源を見ることができるように配置されるＲＢＧ光源とを含むディスプレイデバイス。 In the present specification, the following embodiments are specifically considered.
(Embodiment 1)
Coordination complex represented by the following formula:

In the formula, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^3' , R ^4' , R ^5' , and R ^6'' is independently H or C _1-3 alkyl, L ¹ is F, Cl, Br, or I, L ² is an arbitrarily substituted cyclopentadiene anion, R ^{1 in the formula.} , R ³ , R ⁵ , and R ⁷ are _{not CH 3} , or at least one of ^{R 2} and R ^{6 is not H.}
(Embodiment 2)
The coordination complex according to embodiment 1, wherein R ² is C _{1-3 alkyl.}
(Embodiment 3)
The coordination complex according to embodiment 1 or 2, wherein R ⁶ is C _{1-3 alkyl.}
(Embodiment 4)
The coordination complex according to the first embodiment, that is,

Or a mixture of them.
(Embodiment 5)
A coordination complex containing an arbitrarily substituted 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene and iridium, and an optical filter containing a polymer matrix, wherein the coordination complex is the polymer. Distributed in the matrix
The filter is an optical filter having a quantum yield of less than about 1%.
(Embodiment 6)
An optical filter comprising the coordination complex according to embodiment 1, 2, 3, or 4 and a polymer matrix, wherein the coordination complex is arranged in the polymer matrix.
The filter is an optical filter having a quantum yield of less than about 1%.
(Embodiment 7)
The optical filter according to embodiment 5 or 6, wherein the polymer matrix comprises poly (methyl methacrylate) (PMMA).
(Embodiment 8)
The optical filter according to embodiment 5, 6 or 7, wherein the polymer matrix is in the form of a layer having a thickness of about 0.1 μm to about 50 μm.
(Embodiment 9)
The optical filter according to embodiment 5, 6, 7, or 8, wherein the filter has a peak absorption greater than about 515 nm.
(Embodiment 10)
The optical filter according to embodiment 9, wherein the filter has a peak absorption greater than about 522 nm.
(Embodiment 11)
The optical filter according to embodiment 5, 6, 7, 8, 9, or 10, wherein the filter has a full width at half maximum (FWHM) of less than about 50 nm.
(Embodiment 12)
The optical filter according to embodiment 11, wherein the filter has a FWHM of about 20 to about 30 nm.
(Embodiment 13)
A display device comprising the optical filter according to embodiment 5, 6, 7, 8, 9, 10, 11, or 12, and an RBG light source arranged so that the RGB light source can be seen through the optical filter.

The following are examples of several methods used to make and use the compounds described herein.

Example 1
Synthesis of BODIPY materials
8-1. Synthesis example
Example 1.1
Scheme 1.1. Synthesis of BODIPY compound 1

Synthesis of BODIPY Compound 1: 4- (pyridin-2-yl) benzaldehyde (1 g, 5.46 mmol) and 3-ethyl-2,4-dimethyl-1H-pyrrole (1.34 g, 10.92 mmol), round bottom. It was dissolved in dichloromethane (80 mL) in a flask. Trifluoroacetic acid (2 drops) was added to the reaction mixture and stirred at room temperature for 12 hours. The completion of the reaction was monitored by LC-MS (APCI, mz412). After the reaction was complete, DDQ (1.24 g) was added to the reaction mixture and dipyrromethane was oxidized to produce dipyrin. The reaction was stirred at room temperature for 30 minutes and the completion of the reaction was confirmed by LC-MS (APCI, mz410). Upon completion, the reaction mixture was filtered through Celite and the filtrate was transferred to a round bottom flask. _{Triethylamine (4.6 mL) and BF 3} · Et ₂ O (6.1 mL) were added to the reaction mixture in a round bottom flask containing the filtrate, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was then refluxed for 1 hour and the completion of the reaction was confirmed by LC-MS. When the reaction was complete, the solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography (Combi-flash) with a dichloromethane / hexane eluate at a dichloromethane gradient of 0% -50%. Fractions containing the desired product (confirmed by TLC) were then combined and concentrated to give a dark red solid (0.586 g). The desired product was confirmed by LC-MS (APCI): mz458.

Scheme 1.2. Synthesis of iridium tether type BODIPY complex 1

Synthesis of iridium tethered BODIPY complex 1: BODIPY compound 1 (0.1 g, 0.218 mmol) and dichloromethane (30 mL) were placed in a round bottom flask. Sodium acetate (43 mg, 0.519 mmol) and [IrCp * Cl ₂ ] dimer (87 mg, 0.109 mmol) were added to the reaction flask. The reaction mixture was stirred at room temperature overnight. The next day, the reaction mixture was filtered through Celite and the filtrate was concentrated to give a crude product. The crude product was then purified by silica gel column chromatography (Combi-flash) with dichloromethane / hexane with a gradient of 0% to 100% dichloromethane to elute the residual starting material. The eluate was then changed to 100% ethyl acetate to elute the desired product. The fractions containing the desired product (confirmed by TLC) were then combined and concentrated to give the iridium tethered BODIPY complex 1 as an orange solid (73 mg) confirmed by LC-MS (APCI, negative mode) mz819. Obtained.

Example 2.1 Preparation of filter layer The glass substrate was substantially prepared by the following method. A 1.1 mm thick glass substrate was cut into a size of 1 inch x 1 inch. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with fresh DI water and sonicated for about 1 hour. The glass was then immersed in isopropanol (IPA) and sonicated for about 1 hour. Then, the glass substrate was immersed in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried at room temperature with nitrogen gas.

A 25 wt% solution of a poly (methylmethacrylate) (PMMA) (average molecular weight 120,000 by GPC, manufactured by Sigma-Aldrich) copolymer in cyclopentanone (99.9% purity) was prepared. The prepared copolymer was stirred at 40 ° C. overnight. [PMMA] CAS: 9011-14-7, [Cyclopentanone] CAS: 120-92-3

The 25% PMMA solution (4 g) prepared above was added to a 3 mg iridium tethered BODIPY complex prepared as described above in a sealed container and mixed for about 30 minutes. The PMMA / chromophore solution was then spin-coated on the prepared glass substrate at 1000 RPM for 3 seconds, then at 1500 RPM for 20 seconds, and then at 500 RPM for 2 seconds. The wet coating obtained had a thickness of about 10 μm. The sample was covered with aluminum foil prior to spin coating to protect it from exposure to light. Three samples were prepared in this way, respectively, for each quantum yield and / or stability study. The spin-coated sample was baked in a vacuum oven at 80 ° C. for 3 hours to evaporate the residual solvent.

A 1-inch x 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed in a nitrogen-filled glove box. The obtained absorption spectrum is shown in FIG. The maximum absorption was normalized to about 100% at a wavelength of 522 nm (maximum perceived absorbance wavelength), and the full width at half maximum (FWHM) at maximum absorption was 25 nm.

The fluorescence spectra of the 1-inch x 1-inch film samples prepared as described above were set to their respective maximum absorbance wavelengths using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA). It was determined by the excitation wavelength.

The quantum yields of the 1-inch x 1-inch samples prepared as described above were measured using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell, CA, USA) set for each maximum absorbance wavelength. It has been determined. The quenching compounds of the present invention were weakly fluorescent or essentially non-fluorescent.

For the compound life / stability of the film, a 1-inch x 1-inch film sample (a film containing BODIPY complex 1 or BODIPY-Ir complex 1) is placed in a vacuum oven at 80 ° C., and the absorbance of the sample is periodically measured by a UV-Vis spectrometer. It was decided by confirming the target. After 527 hours, the absorbance was about 87% of the original absorbance (see Table 1). In another example, a 1 inch x 1 inch sample was placed in ambient air in an oven at 85 ° C. After 509.5 hours, the absorbances were about 80% and 64%, as shown in Table 1.

The results of film characterization (absorption peak wavelength, FWHM, and quantum yield) are shown in Table 1 below.

Therefore, at least the BODIPY-1 iridium complex appears to be quenched in quantum yield after tethering the BODIPY moiety to iridium, demonstrating its effectiveness as a useful filter material for display devices.

Those skilled in the art will appreciate that a number of various modifications can be made without departing from the spirit of the invention. Therefore, it should be clearly understood that the embodiments of the present invention are merely exemplary and are not intended to limit the scope of the invention.

Unless otherwise indicated, all numbers used in this specification and in the claims to describe properties such as molecular weight, molecular weight, reaction conditions, etc. are modified in all cases by the term "about". Should be understood. In contrast, the numerical parameters described herein and in the appended claims are approximations that can vary depending on the desired properties to be obtained. At least, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical parameter is at least interpreted by applying the usual rounding method, taking into account the number of significant figures reported. Should be.

The terms "a", "an", "the", and similar referents used in the context of describing the inventions of the present disclosure (particularly in the context of the following claims) are referred to herein. Unless instructed or explicitly denied by the context, it should be construed as covering both singular and plural. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or expressly denied in context. The use of any example, or exemplary language (eg, "such as") provided herein is solely for the purpose of better illustrating embodiments of the present disclosure, and any claim. The range of is not limited. No language in this specification should be construed as indicating any unclaimed element essential to the implementation of the embodiments of the present disclosure.

The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Members of each group may refer to and claim individually or in any combination with other members of the group or other elements found herein. It is expected that one or more members of the group will be included in or removed from the group for convenience and / or patentability reasons. If such inclusion or deletion occurs, the specification is deemed to include the modified group and meets the description of all Markush groups used in the appended claims.

Specific embodiments are described herein, including the best embodiments known to us to carry out the invention. As a matter of course, modifications to these described embodiments will become apparent to those skilled in the art upon reading the above description. The inventors anticipate that those skilled in the art will appropriately use such variants, and we present the present invention in a manner different from that specifically described herein. It is intended to carry out the disclosed invention. Therefore, the claims include all modifications and equivalents of the subject matter listed in the claims, as permitted by applicable law. Moreover, any combination of the above elements in all possible variants thereof is envisioned unless otherwise indicated herein or expressly denied by the context.

Finally, it should be understood that the embodiments disclosed herein are examples of the principles of the claims. Other changes that may be used are within the claims. Thus, as an example, but not a limitation, alternative embodiments may be utilized as taught herein. Therefore, the scope of claims is not limited to the exact embodiments shown and explained.

Claims (14)

Coordination complex represented by the following formula:

In the formula, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ^2' , R ^5' , R ^6' , R ^3' , R ^4' , R ^5' , and R ^6'' is independently H or C _1-3 alkyl, R ⁶ is C _1-3 alkyl, L ¹ is F, Cl, Br, or I, and L ² is optionally substituted. Ru cyclopentadiene anion der. The coordination complex according to claim 1, wherein R ² is C _{1-3 alkyl.} The coordination complex according to claim 1 , wherein the coordination complex is

Or a coordination complex that is a mixture thereof. The optical filter including the coordination complex according to claim 1, 2 or 3 , and the polymer matrix, wherein the coordination complex is arranged in the polymer matrix.
The filter is an optical filter having a quantum yield of less than 1%. The optical filter according to claim 4 , wherein the polymer matrix contains poly (methyl methacrylate) (PMMA). The polymer matrix is 0 . The optical filter according to claim 4 or 5 , which is in the form of a layer having a thickness of 1 μm to 50 μm. The optical filter according to claim 4, 5, or 6, wherein the polymer matrix is in the form of a layer having a thickness of 10 μm. The optical filter of claim 4, 5, 6, or 7, wherein the filter has a peak absorption greater than 515 nm. The optical filter of claim 8 , wherein the filter has a peak absorption greater than 522 nm. The optical filter according to claim 4, 5, 6, 7, 8 or 9, wherein the filter has a full width at half maximum (FWHM) of less than 50 nm. The optical filter according to claim 10 , wherein the filter has a FWHM of 20 to 30 nm. The optical filter according to claim 10 , wherein the filter has a FWHM of 25 nm. A display device comprising the optical filter according to claim 4, 5, 6, 7, 8, 9, 10, 11, or 12, and an RBG light source arranged so that the RGB light source can be seen through the optical filter. .. 4.4-Difluoro-4-bora-3a, 4a-diaza-s-indacene and iridium according to claim 1, 2 or 3, wherein the coordination complex is optionally substituted. A coordination complex containing a coordination complex containing the same, and an optical filter in which the coordination complex is dispersed in the polymer matrix and contains the polymer matrix.
The filter is an optical filter having a quantum yield of less than 1%.

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